In this work, a new approach for TMPyP [5,10,15,20-tetrakis (1-methylpyridinium-4-yl) porphyrin] and TMAPP [5,10,15,20-tetrakis (N,N,N-trimethyl-anilinium-4-yl) porphyrin] intercalation into α-phase of zirconium hydrogen phosphate (α-ZrP) was described: porphyrins were inserted through exchanging pre-intercalated alkylamine. Pre-intercalated n-butylamine (BA) could form either a mobile monolayer or a stable bilayer in α-ZrP. The exchange speed between porphyrins and BA in mobile monolayer is obviously faster than that in stable bilayer. Therefore mobility of spacers is one important intercalation factor. In addition, we investigated the interlayer state of TMPyP by XRD, visible spectrum, fluorescence spectrum and molecular modeling. The results collectively revealed that the porphyrin was orderly arranged with their planes inclined to the host lamella and was presented as monomer instead of aggregation in the gallery of α-ZrP.